Anthraquinone compounds



Patented Dec. 30, 1947 UNITED PATENT OFF 2,433,553 ICE 2,433,551 ANTHRAQUINONE CUMPOUNDS Ernst Gutzwiller, Basel, Switzerland, assignor to 'Sandoz Ltd, Fribourg, Switzerland No Drawing. Application April 21, 1942, Serial No. 439,942. In Switzerland December 24, 1940 Section 1, Public Law 690, August 8, 194.6 Patent expires December 24, 1960 4 Claims.

spectively. -7-halogenanthraquinone compounds is carried out according to the literature by start--- ing from 1-alkylamino-4-bromo-6- or -'l-halogen anthraquinones respectively, condensation of these compounds with toluene sulfamide and subsequent saponification of the sulfotolyl group. The processes above cited need, therefore, several operations before the desired products can be obtained (see U. S. Patent 2,134,654).

According to the present invention these and other new anthraquinone compounds can be prepared by condensation of anthraquinone compounds of the general formula or their leuco compounds, wherein X and W stand for replaceable substituents, Y and Z stand for halogen, or one of the same for a halogen and the other one for hydrogen, with amines of the formula HzN-R, wherein R stands for hydrogen, alkyl and hydroxyalkyl.

In order to prepare the products of the present new process the above cited anthraquinone compounds or their leuco derivatives are heated with the amines at a temperature which is generally between 50 and 200 C. Generally, the condensation is carried out in the presence of diluents like water, methanol, ethanol, aromatic and hydroarornatic hydrocarbons and, in order to accel-' erate the reaction, there is added for instance alkali metal hydroxides, bicarbonates, carbonates or acetates to the mixture. Sometimes, it'is useful to add a small amount of for example copper salts or of boric acid. When the amines used are easily volatile, it is preferable to work in a closed vessel, in order to avoid a loss of the reagents. The isolation of the condensation products is carried out in the usual manner and need not be specifically described.

In this manner and thus in a very simple way anthraquinone compounds can be prepared, while the manufacture thereof according to the method bf the U. s. Patent 2,134,654 need diiierent and complicated steps. Further, it is possible to prepare by the present process very valuable dialkylaminoor dihydroxyalkylamino-, or alkylaminohydroxy-alkylamino compounds, which possess very valuable technical properties. The anthraquinone derivatives obtained by the present process are suitable forthe dyeing of organic solvents like petroleum, oils and the like and of plastical omasses as 'well as of acetate rayon. As compared to the known anthraquinone compounds of similar constitution which do not contain in 6- and/ or 7-position halogen atoms, the compounds prepared by thepresent process possess the advantage to have a very good shade in the artificial light.

The following examples, without being limitative, illustrate the present process, the parts being by weight.

' Example 1 23 parts of 6-chloroquinizarine, 20 parts of sodium hydrosulfite and 90 parts of aqueous ammonia of 25% strength are heated during 6 hours in an autoclave at 80-100 C. The leuco-1:4-diamino-6-chloro-anthraquinone thereby produced can be isolated by filtration and, after washing with water, is dried. It can be transformed into 1:4 diamino 6 chloroanthraquinone by the known methods, e. g., by heating in an air stream at 180 C. or by oxidation, for instance with manganese peroxide in sulfuric acid. The 1:4-diamino-6-chloroanthraquinone dyes acetate rayon in beautiful violet shades.

By using instead of the 6-chloroquinizarine '6:7-dichloroquinizarine, the 1 l-diamino-6i7-dichloroanthraquinone is obtainedl Example 2 7 parts of leuco-6-chloroquinizarine, 3 parts of 6-chloroquinizarine, 30 parts of methylamine 40% and 80 parts of ethanol are heated at 80 C., until no more unchanged fi-chloroquinizarine can be detected. For the oxidation of theleuco compound air is blown on the surface of the reaction charge, eventually after addition of some pyridine. After cooling down the reaction product is Example 3 10 parts of leuco-G-chloroquinizarine, 15 parts of monoethanolamine and parts of ethanol are 3 stirred at 80 C.,-,until=the leuco-chloroquinizarine has disappeared? After cooling down; the'reaction product is filtered and washed with ethanoL. The 1 i-dihydroxyethylamino-6-chloroanthraquinone thus obtained dyes acetate rayon in -very 6* bright greenish-blue shades of. excellent shadesin the artificial light and of good fastness toli hth Example 4.

9.2 parts of leuco-6-chloroquinizarine; 2i3parts of monoethanolamine, 3.2 partsiofimethylamine' 40% and 50 parts of ethanol are stirred at 65 1f,

until the reaction has completed. After addition= of 0.5 part of pyridine airis blown into the reaction mixture, the condensation product filtered after-cooling down and washed'with" ethanol.

The. 1: 4-methylaminohydroxyethylamino;6; or -'T-chlor0.anthraquinone'- respectively." thus" obtained dyes acetate rayon in brilliant greenish blue sh'adesrof excellentshade at the'artifi'cial light.

Example: 5.

10 partsof" leu'co-6 f'l' dihloroquinizarlne; n"

parts of monoethan'olamine and 80 parts of ethanol are stirred at-80 'C.-, until-the condensa tion hascompl'etedi Then, if necessary; air is blown over the surface of the reaction mixture',. eventuallyafteraddition of- 'some parts-of pyridine or piperidine, I in order to produce the oxidation; The dihydroxyethyl amino- 6% 7- dichloro anthra'quinone so obtained dyes organic solvents. and acetate rayon in greenish-blue brilli'ant'sha'des.

Example 6 10 parts of leuco-6 -chloroquinizarine, 15 parts of amylamine, 7 parts of boric acidand 80 parts of' amyl alcohol are stirredat 80 120" 'Ci, until the condensation-hasfinished: The lziltr'diamyl amino-G-ch-loroanthraquinone is separated by filtration it dyes organic solvents like"p'etrol,i oil and thelike ingreenish-blue shades.

By using instead of leu'co-firchloroquinizarine. the leuco-fit'l diohloroquinizarine, the 1":4-di amylamino-G:7-dichloroanthraquinone. is obtained.

Example? 10 parts of leuco-fi:Rdichloroquinizarine, 15' parts of aminodioxypropaneand 80- parts' of ethanol arestirred at 80 (2., until the leuco-61'71- dichloroquinizarine has disappeared; 'I'heleuco- 1 :4-di (dihydroXy'propylan'iino) 6 T-dichloroanthraquinone is oxidized byastream of air after addition of 0.5, part of pyridine. After cooling down; the new product is filteredioff. andwashed with alcohol.

The 1 :4-di- (dihydroxypropylamino) 6 :7T-dichloroanthraquinone dyies' acetate rayon in. bril liant greenish-blue shades.

4 alkali? alkali. metal carbonates E or; alkalimetal acetates and eventually of metal 'salts.

What I claim is: 1. An anthraquinone compound of the formula g NH-R wherein R stands for the same member of the group 'consisting of alkyl and hydroxyalkyl, and at least one of Y and Z stands for C1, the other onerotY, and 2 standing-"for a memberifofthe group consisting of hydrogen and'Cl, saidv com-- pound being soluble in organic solvents. and: dyeinggaoetate rayon ini violet to blue shades;

2.1 An ant-hraquinona compound oftheformula 0 NH- lt NE-R wherein R standsjfor the same member. of'the group" consisting'of a kyl and hydroxylalkyl', said compound being" soluble in organic solvents and dyeing' acetate rayon in violet, to blue shades.

3' Thean'thraquinone compound of the formula" NHL] Ha ll 0 Nnom.

which is soluble in organic solvents and dyes acetate rayon in blue shades.

4. The anthraquinone-compound of the formula ERNST GUTZWILLER.

REFERENCES CITED The following references: are of record in the fileof. thiapatent:

UNITED STATES PATENTS Number Name Date 1,014,204 B'erchelmann- Jan. 9, 1912. 1,543,313 Baumann Feb. 2, 1932 2,05,16'62 Koeberle Aug; 11, 1936 2,092.39? Koeberle Sept. 7, 1937 2.13%,654. Lulek Oct. 25-, 1938 2,211,943} Wilder Aug. 20, 1940.

FOREIGN PATENTS Number" Country. Date.

51018' Great Britain 1899 221,929 Switzerland Sept. 16, .1942

OTHER. REFERENCES Patent Laws of the World, by the Chartered Institute'of Patent Agents (London 1911'), vol. 2, pages57 7; 578 

